Metal-containing polyazo dyestuffs



United States Patent METAL-CONTAINING POLYAZO DYESTUFFS MarkusKappeler and August Schweizer, Basel, Switzerland, assignors toSandoz. A. G., Basel, Switzerland, a Swiss firm No Drawing. Application December" 1 8, 1953, Serial No. 399,156

Claims priority, application Switzerland December 24, 1952 6 Claims. (Cl. 260-145) The present invention relates to new metal-containing polyazo 'dyestufis.

A' primary object of the invention is the -embodiment of metal-containing polyazo dyestuffs of especial utility in the idyeing of leather. This object-is realized by the dyestuifs according'to :the invention, which correspond to the formula no if) q 'SIO'SH 503E =NR-a wherein w stands for a hydrogen atom or a N=N- mononuclear radical, x stands for a CH=CH- or CH2CH2-bridge, .z-is .a H simple linkage or stands for azo-R1, in Which'R1 denotes a monoor binuclear radicalof the benzenelserics or aradicalof the naphthalene series, -azo- 'being located in one ofthe positions meta'and parato the respective 'N='N- group, R stands for a monoor binuclear radical of the benzeneser-ies or a radical of the naphthalene series, R'astands for a radical of the benzene series, in which a is a substituent capable of favouring metal complex formation and is present in ortho-position to the respective N=N group, and which radical may further be'substituted'for instance by water-solubilizing;groups, e..g. the sulfonic acid or sulfonic acid aminev group, Me stands for a heavy metal atom, and wherein n is one of the numerals 1 and 2.

The new metal-containing polyazo dyestufls are obtained by coupling 1 mol of the diazo compoundfrom an aminoazo dyestulf of the composition A0311 OaH wherein x and R have the previously cited significance, and y is an amino group or the radical -azo-RiNH2, in which R1 denotes a monoor binuclear radical .of the benzene series or aradical of the naphthalene series, azobeing located-in one of the positions meta'and para to NH2, with l'rnol'of a monoazo compound of the composition wherein Ra has the previously cited significance, and treating the polyazo dyestuft thus obtained with a metalyielding agent.

It is possibleto'introducethemetal atom'alreztdyin thecoupling of the 'diazotized aminoazo dyestuflf (I) with the monoazocompound (II) by taking, for exampleflthe monoazo compound (II) in the form of its metal complex for coupling with the diazo compound 2,749,333 Patented June: 5, '1-956 "ice ' formation.

Valuablepolyazo#dyestuifs can also *be'obtained if the end product is coupled with at most 1 mol of diazotized aminobenzene compound before or after treatment with a metallizing agent.

The sulfonamide groups which can be present in residue R can be substituted on the nitrogen 'atom, whereby as 'sub'stituents lower molecular "alkyl groups come' iiijt'o favourable 'consideratiomwhich on their part can be substituted by hydroxyl or alkoxy'groups.

'According to'a further method of carrying .out'theinvention, polyazo dyestuffs can also be prepared'by coupling 1 mol of the diazo compound from" an aminoazo dyestufi of composition (I) first with 1 mol of 1:3- dihydroxybenzene and then coupling the product *obtained with 1 mol-of the diazocompound from an aromatic amine of the composition wherein:R' -b stands-for -a radicaI of the' benzene series,

--b-being a substituent capable offavouring metal complex formation and being present in ortho-position to NHz, and then treating the polyazo dyestuff thus obtained with a metal-yielding agent.

Also in this method of carrying out the process it is possibleto couple thezpolyazo dyestufl withz at most l mol of a diazotized aminobenzene compound before-or after treatment with a 'metakyielding agent.

If the symbol b denotes a hydroxy group as the group capable of favouring metal complexformationthis'group can alsobe closed by an alkylsulfonyl or arylsulfonyl radical. If this is the case then the alklysulfonyl or arylsulfonyl radical must be split off before treatment of the end product with a metal-yielding agent.

The aminoazo dyestuif of composition (I) is advantageously diazotized indirectly and the coupling of the diazo'compound thus obtained 'with 'the azo coupling component (II) according tothe first'form of carrying out the invention is generallyelfected in weakly alkaline solution. The coupling of the diazo compoundwith 1 33- dihydroxybenzene according to the "secondmethod'of carrying out the invent-ion takes 'place"advantageously in a neutral to alkalinemediumandthat of the intermediate products "thus obtained 'with diazotized aromatic amines "of formula (III) likewisetakes place with advantage in an alkaline medium. The polyazo dyestufis obtained are worked up in the usual manner -'by salting out from the reaction solution, filtration, washing and drying.

The new dyestuifs can, according to the presentiinventionfbe obtained "directlyas metalcomplex compounds. As complex forming metals chromium, cobalt and nickel *are very suitable, but most especially copper. If the polyazo dyestuffs are to be converted subsequently into their metal complex compounds then their metallization takes place advantageously with chromium, cobalt or nickel compounds and in particularwith copper-yielding agents. The coppering-can take place according to the most varied methods-known from the literature as, for instance, by heating the 'dyestuif'with'copper salts in weakly acid to alkaline medium, if desired with the use of pressure and in the presence of ammonia or organic bases, or in the melt or alkaliasalts of lower molecular HMOMNOMNQ leather and semi-chrome leather, on chrome tanned, chrome syntan or chrome vegetable tanned glove leather as well as on pure vegetable tanned leather. Furthermore they give on suede leather well penetrated brown shades which are fast to bufiing. It may be emphasized that the dyestuffs possess a most excellent power of fixation on these various types of leather.

The following examples illustrate the invention.

If the resultant polyazo dyestuff before its isolation is coupled with 1 mol of diazotized l-amino-4-nitrobenzene2-sulfonic acid then a dyestuff is obtained which corresponds to the formula and dyes leather in neutral brown shades of similar properties.

EXAMPLE 2 If in the previous example, the 37.2 parts of the coupling component are replaced by 41.6 parts of the copper complex compounds of 2.2'.4-trihydroxy-5-nitro- 1.1-azobenzene-3-sulfonic acid, then a similar dyestutf Therein the parts denote parts by weight, the percentages is obtained. It corresponds to the formula denote percentages by weight, and the degrees are in degrees centigrade.

EXAMPLE 1 64.3 parts of the amino-disazo dyestuff of the formula EXAMPLE 3 are dissolved in the form of the sodium salt thereof in 1000 parts of water, and are diazotized by the addition of a solution of 7 parts of sodium nitrite in 20 parts of water and parts of 30% hydrochloric acid at 10. The solution of the diazo compound is run into an icecooled solution of 37.2 parts of the copper complex compound of 2.2.4-trihydroxy-l.1'-azobenzene-5-sulfonic acid and 40 parts of sodium carbonate in 400 parts of water. After coupling is completed, the resultant polyazo dyestuff is separated out by the addition of sodium chloride, filtered off and dried. It corresponds to the formula and dyes chrome suede leather with excellent power of exhaustion and good penetration power in brilliant reddish-brown shades. The dyeings are very fast to buffing and have good fastness to light.

0H whoa MQCHHQMQ I 0m 0m N==N obtained which dyes crome suede leather in bright brown shades fast to bufiing and to light.

EXAMPLE 4 The dyestuff, obtained according to the method of Example 1 but using 36.0 parts of the chromium complex compound of 2.2.4'-trihydroxy-l.l-azobenzene-5-sulfonic acid instead of 37.2 parts of the respective copper compleX compound, dyes chrome suede leather in yellowishbrown shades fast to butting.

EXAMPLE 5 If the coupling component of Example 1 is replaced by 36.7 parts of the corresponding nickel complex compound, then the nickel-containing polyazo dyestuff is obtained. It corresponds to the formula and dyes chrome suede leather in reddish-brown shades fast to bufling and to light.

EXAMPLE 6 47.5 parts of thei-aminot-monoazo dyestufiv-ofaformula are diazotized according to the method of Example 1. Thesolution of the diazocompound is run.into a solution"of 11"parts'of113 dihydroxybenzene,35 parts of sodium carbonateand 200ipartsxof water. :After coupling has ensued, a further 40 parts .of sodiumcarbonate .are

added-twthe solution. A'solution'of the diazo compound from 18.9 gpar-ts-of '1l-hydroxy-2-arninobenzene-4- sulfonic acid is then added thereto. After coupling is in 500 partsofwater. er coupling is'complete, the resultant polyazo dyestufi is isolated and is filtered off. The filter cake is then heated for several hours in aqueous solution and in thepresence of ammonia and copper sulfate. The formation of the polyazo dyestuff containing 2 atoms of copper thereby ensues with splitting of. the methoxy groups. 'The .coppered. products-separated .out by ithe addition of. sodium chloride is filtered olfand dried. It corresponds to the formula O-Cu'0 QO-Cu-O 1 m soar 1H, -N=N i OaH and dyeschrome' suede'leather in'deep-dark brown'shades.

EXAMPLE '8 47.7 parts of the amino-monoazo dyestuifof-the formula are dissolved in the form of its sodium salt in 800,,parts of water and diazotized by the addition of 7 parts of sodium nitrite and 30 parts of 30% hydrochloric acid. Thediazo solution is run into a solution of.37.2.parts of the copper complex compound from 2.2.4'-trihydroxy-1.1-azobenzene-S-sulfonic acid in. parts ofsodium carbonate in 450 parts of water. "The resultant copper-containing polyazo dyestutf'is precipitated out from the solution by the addition of sodium chloride and is .filtere'd off and dried. It corresponds to the formula stufi formed'is salted out, filteredoif and dried. It corresponds to the formula and is a dark brown powder which dyes chrome suede leatherxin bright.reddish=brownshadesifast @to buifing.

EXAMPLE 7 60 79.1 parts iOf the amino-trisazo dyestufi of the formula are diazotized-according to the data of Example 1. The solution of the diazo compound is run into:an ice-cooled solution of 32.2 parts of 2-methoxy-2.4'-dihydroxy 1.1'-

OgH

Land is a brown powder 'which dissolvesin water witha brown color and dyes chrome suede leather :in brown shades.

EXAMPLE 9 A polyazo dyestuff which dyes chrome suede leather OCH;

OsH CH;

afsomewhat deeperbrown than thafobtainable according *to the previous examples is obtained if the 47.7 parts of the..aminomonoazo dyestutf of the foregoing example is azobenzene-S-sulfonic acid and 40 parts sodium carbonate 7 replaced by. 62.5: parts of the aminoedisazo :dyestufi. of

OCH:

HO MMQCHPOHQMQNH.

OIH 0011 H:

7 In the resultant polyazo dyestutf of the formula OCH on I BOON: QCHPCHN=N-QN=N oou-o om 0.11 H. N-N

a second atom of copper in complex combination can be introduced with splitting of the methoxy group, whereby a dyestufi is obtained which dyes chrome suede leather in dark brown shades.

The following Table 1 includes further metal-containing polyazo dyestuffs which can be obtained according to one of the methods of working described in the previous examples. Therein the aminoazo dyestuffs of formula (I) are shown in column (A), and the monoazo compounds of formula (II) present as copper complexes are shown in column (B). The column (Aa) gives the aromatic compound R-H which corresponds to the radical R contained in the formula (I) preparation and the column (C) gives the shade of dyeing ==N X of the copper complex compounds on chrome suede 25 leather.

Table 1 ExlaImple (All) (Ab) y Copper complex compound from 10 benzene(l)-4sulfonle acid NH 2.2 .4'-trihydr0xy-3-carb oryl.1- brown.

azobenzene-S-sulionic acid. NH| 2.2.4'-trihydroxy-l.1'-azobenzene-5- reddish-brown.

sulionic acid amide. NH: 2.2'.4-trihydroxy-1.1azobenzene-5- Do.

sullonic acid methylamide. NH: 2.2.4-trihydroxy-l.1-awbenzene-5- Do.

sulfonic acid (B-hydroxy)-ethylamide. -NH1 2.5- dimethoxy-2 .4 -dihydroxy-1.l' Do.

nzobenzene-i-sulionic acid. -NH1 2.2 4 -trihydroxy-5-ethoxy-1.1-azo- Do,

benzene-4-sulfonic acid. -NH: 2.2.4-trihydroxy-l.l-azobenzene-5- brown sulfonic acid. benzene (1)-3-sulfonic acid -NH| D0. nuphthaIene(1)-6-sulfonic acid NH1 D0. naphthalene(2)-4.8-disull0nio N Do. 4-methoxybenzene(1) -NH, .--d0 Do. 4 hydroxybenzenefl) 3-carboxyllc -NH: 2.2 A'-trihydroxy 3 nltr Do.

acid. benzene-5-sulionlc acid. 1 hydr0xynapl1thalene(2) 3.6 di -N d red-brown.

sullonio acid. 2 hydroxynaphthalenefl) 3.6 di NH: Do.

sultonlc acid.

benzene(1)-4-sul1'onie acid -N-N-- NH: 2.2.4'- trlhydroxy 1.1'- azobenzene' brown'.

, 6-sultonlc acid.

O CH

25... --N-N NH: .-...do Do.

O O OH 26 ..do -N-N NH .....do Do.

G O OH 27 benzene(1)-4-carboxylic acid -N=N NH: .do Do.

0 28 benzene(1)'3-sul!onic acid N--N .....do Do.

9,749,833 1 1 1 2 The dyestuffs of Examples 25, 29, 43, 44 and 48 can be tion of the dye-bath the chrome suede leather is withfurther coppered in substance with simultaneous dealkyldrawn and rinsed in water. ation, whereby the dyeing shade of their dyeings on Having thus disclosed the invention what is claimed is: chrome suede leather is shifted towards deep brown. 5 l. A polyazo dyestuff which corresponds to the formula Also the dyestuffs of Examples 21, 26, 27 and 47 can, wherein w stands for a member selected from the group in substance as well as on the fiber (e. g. fibers of celluconsisting of a hydrogen atom and a N=N- monolo b f th COPPered, Thg color of h d i i nuclear aryl radical, x stands for a bridge selected from in this case only slightly shifted towards deep brown. the group 60115151138 0f and CH2-CH2- Table 2 (A) Example No.

(All) RH= (Ab) y:

51 benzene(1)4-sulfonic acid- NH1 2-carboxy-2.4'-dihydroxy- Brown.

Llgazobenzene-l-sultonlc aci 52 do NH: Z-csrb0xy-2.4-dihydroxy- Do.

1.1'-azobenzene-4-sulionlc acid amide.

EXAMPLE 53 R stands for a member selected from the group consisting of a mononuclear and a binuclear radical of the benzene series and a radical of the naphthalene series, R" stands for a member selected from the group consisting 100 parts of well neutralized chrome calf leather are 30 entered in a vat containing 200 parts of water of 60". A

l t' f l t of th 01 d stuff bta' d ac- :g f; fgg 1 gi i gg in of a mononuclear and a blnuclear radical of the benzene two or three portions within 15 minutes. After series and a radical of the naphthalene series, and -azominutes the dye vat is treated with 1.8 parts of 10% bung located m one of the Posmons meta and P formic acid. The product is milled for a further 20 l respective f g stands f a minutes and the chrome calf leather is thereupon lcal of the benzene series, in which a is a substituent seliquored in a fresh bath in the usual manner. lected from the group consisting of q methoxy and carboxy and 13 present in ortho-position to the re- EXAMPLE 54 spective N=N- group, Me stands for a metal atom 100 parts f chrome suede leather mined with selected from the group consisting of a chromium, co-

of concentrated ammonia and 0.5% of a non-ionic wetball, nickel and PP atom, and wherein m and each ting agent, are entered in a vat containing 500 parts of is 8 0f h numerals 1 and 2.

water of To the rotating dye-bath there is added 2- The polyazo dyestutf which corresponds to the forthrough the hollow axis a solution of 8 parts of the dyemula OH HQISON=NON=NQCH=CH-QN==NQo ou-o 0,11 OIH 0,151

stufi obtained according to Example 1 and 2 parts of 3. The polyazo dyestufi which corresponds to the forconcentrated ammonia in 2400 parts of water. When a mula 0H H0 M MQCMHQNZNQ H i I our on:

sufficient dyeing penetration is obtained, parts of 5% 4. The polyazo dyestuff which corresponds to the forformic acid are added to the dye-bath. After exhausmula I 0.11 on: N===N 2,749,333 13 14 5. The polyazo dyestuff which corresponds to the formula 03H 05H N=N 6. The polyazo dyestuif which corresponds to the formula 0Cu-O 0,11 0311 (EH; Q

OzH

References Cited in the file of this patent UNITED STATES PATENTS 2,197,350 Schindhelm et a1. Apr. 16, 1940 2,518,020 Kappeler Aug. 8, 1950 2,574,782 Gunst Nov. 13, 1951 2,673,200 Ruckstuhl et a1. Mar. 23, 1954 FOREIGN PATENTS 674,708 Great Britain Jan. 25, 1952 

1. A POLYAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA WHEREIN W STANDS FOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF A HYDROGEN ATOM AND A-N=N-MONONUCLEAR ARYL RADICAL, X STANDS FOR A BRIDGE SELECTED FROM THE GROUP CONSISTING OF -CH=CH- AND 